Long chain ether alcohol sulfates from propylene oxide and 1,2-butylene oxide

ABSTRACT

The present invention is directed to long chain ether alcohols and alcohol sulfates from propylene oxide and 1,2-butylene oxide having the formula R(OCH2CH(R&#39;&#39;))nOY, wherein R is an n-alkyl radical containing 12 to 18 carbon atoms; R&#39;&#39; is selected from methyl and ethyl; n is an integer from 1 to 4; and Y is selected from H and SO3 M, wherein M is selected from Na, K, Li, NH4 and NH(C2H4OH)3, useful as biodegradable detergents.

United States Patent [191 Weil et a1.

[ LONG CHAIN ETHER ALCOHOL SULFATES FROM PROPYLENE OXIDE AND 1,2-BUTYLENE OXIDE [75] Inventors: James K. Weil, North Wales;

Alexander J. Stirton, Philadelphia, both of Pa.

[73] Assignee: The United States of America as represented by the Secretary of Agriculture, Washington, DC. [22] Filed: Dec. 1, 1971 [21] Appl. No.2 203,867

Related US. Application Data [62] Division of Ser. No. 844699, May 23. 1969. abandoned. which is a division of Ser. No. 557,375, June 14. 1966, abandonedv [52] US. Cl. 260/458, 252/551, 260/615 B [51] Int. Cl. C07c 141/00 [58] Field of Search 260/458 51 Oct. 22, 1974 443,559 2/1936 Great Britain 260/458 OTHER PUBLICATIONS J. Weil et a1., J.A.O.C.S., 43 (3), pp. 157460, (March 1966).

Bistline et al., J.A.O.C.S., 34 (10), Pp. 516-518. (1957).

Primary Examiner-Leon Zitver Assistant Examiner-Norman Morgenstern Attorney, Agent, or Firm-M. Howard Silverstein; Max D. Hensley [57] ABSTRACT The present invention is directed to long chain ether alcohols and alcohol sulfates from propylene oxide and 1,2-butylene oxide having the formula R[OCH CH(R')],,OY, wherein R is an n-alkyl radical containing 12 to 18 carbon atoms; R' is selected from methyl and ethyl; n is an integer from 1 to 4; and Y is selected from H and S0 M, wherein M is selected from Na, K, Li, NH, and NH(C H OH)3, useful as biodegradable detergents.

1 Claim, N0 Drawings LONG CHAIN ETHER ALCOHOL SULFATES FROM PROPYLENE ox p AN!) -aurypnm: OXIDE This is a division of application Ser. No. 844,699 filed May 23, 1969 which is a division of application Ser. No. 557,375, filed June 14, 1966 both now abandoned. A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the U.S. Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to biodegradable detergents. More particularly this invention relates to novel long carbon chain ether alcohol sulfates.

An object of the present invention is to provide readily soluble, easily biodegradable detergents from long chain primary alcohols, particularly those derivable from animal fats. Long chain sodium alkyl sulfates derivable from saturated tallow alcohols, mainly sodium hexadecyl sulfate and sodium octadecyl sulfate, are good detergents at higher washing temperatures. However, because of limited solubility at room temperature or slightly above room temperature they cannot function as the sole active ingredient in household detergent compositions, but they require the presence of a more soluble type of detergent also. The usefulness of the tallow alcohol sulfates is restricted because of limited solubility and they cannot enter into the formulation of a variety of types of detergents, such as liquid detergents or cold water detergents.

Only ether alcohol sulfates based on long carbon chain alcohols and ethylene oxide have been previously prepared. Since propylene oxide and butylene oxide contain more hydrophobic methyl and methylene groups than ethylene oxide, it has been assumed that surface active products derived from them would be less soluble in water and have little use. Quite unexpectedly and contrary to predictions, however, we have discovered that ether alcohol sulfates based on propylene oxide or 1,2-butylene oxide are actually more soluble than corresponding products based on ethylene oxide.

Another object of the present invention is to prepare biodegradable, water soluble anionic detergents that are good lime soap dispersing agents. A further object is to provide chemical intermediates from which to prepare the anionic detergents. Still another object is to prepare anionic detergents which are useful in the form of built compositions.

Other objects and a fuller understanding of the invention will become apparent upon referring to the following description and claims.

The compounds of the present invention can be represented by the formula:

wherein R is an n-alkyl radical containing from 12 to 18 carbon atoms; R is selected from methyl and ethyl; n is an integer from 1 to 4; and Y is selected from H and SO H, wherein M is selected from Na, K, Li, NH.,, and NH(C H,OH)

The ether alcohols of our invention have been found to have an important advantage as anionic detergent intermediates compared to ether alcohols from ethylene oxide. The alkali-catalyzed reaction of a long chain primary alcohol with ethylene oxide produces a first derivative ROCl-l CH Ol-l which is more reactive than the parent alcohol and reacts further with ethylene oxide in preference to reaction of the parent alcohol with ethylene oxide. This behavior is represented as follows:

At any given time, for relatively small values ofn, the reaction mixture will consist of unchanged parent alcohol, the first derivative, and the second and succeeding derivatives in relative amounts which can be predicted from a mathematical expression known as the Weibull- Nycander equation. The distribution constant 0, or ratio of the velocity of reaction (2) to reaction (I) is given as follows:

0 k /k 3.0. In the synthesis of ether alcohol sulfates it is desirable that the value of n be small, suitably in the range n l-3, or else the product has more nonionic than anionic character and is less suitable as a heavy duty detergent. The high value of the distribution constant means that the reaction cannot be directed to relatively high yields of the first derivative. Thus a further object of our invention is to obtain relatively high yields of the ether alcohol first derivative.

We have discovered that, in contrast to the use of ethylene oxide, high yields of the desired ether alcohol first derivative ROCH CHOHCH or ROCH CHOHCH CH are possible with the use of propylene oxide or 1,2-butylene oxide in place of ethyleneoxide. The reaction may be represented as follows:

A k1 ROII CIHLIICII; --t ltUCllzCllOlIUlla k1 ROH CHaCHz HCH; ROCHzCHOHCHzCH:

ROGH CHOHCHzCH: n-wmcmaibm .B Q G WEQI H.

The distribution constants C [Cg/k are found to be 0.5 and 0.3 for oxypropylation and oxybutylation respectively. This means that at relatively low values of n the first derivative is the major component in the reaction mixture, in contrast to what is true for oxyethylation.

Product distribution in oxypropylation was obtained by gasliquid chromatography of the acetates R[OCH Cl-l(CH )],,O- CCH and fractional distillation of the acetates. These two methods were found to agree very well and to coincide closely with the values predicted from the Weibull-Nycander equation. Results obtained in the reaction of propylene oxide with hexadecanol at ll75C in the presence of 0.5 percent potassium hydroxide catalyst, to give a product with an average of 1.20 oxypropyl groups per mole of hex adecanol are shown in Table l. The data of Table l indicate almost a percent yield of derivatives, of which half are the first derivative (n=1). Substantially all of the oxypropylated product falls in the range of n=l to 4, with most of the product having the preferred structure of n=l to 3.

TABLE I 4 ther reaction with ethylene oxide, propylene oxide. or diitylene oxide. 3

The ether alcohols are converted to the improved biodegradable water soluble anionic detergents of the DISTRIBUTION OF PRODUCTS. C H;, [OCH,CH(CH;) In OH. IN THE REACTION OF PROPYLENE OXIDE WITH HEXADECANOL Calculated by the FOUND. mole fractions The analytical values and physical constants for the pure ether alcohols of our invention are shown in Table 11. These are new compounds which have not previously been reported in a pure state.

Comparative freezing points of ether alcohols are an indication of the degree of usefulness of the ether alcohol as an intermediate for the production of more solupresent invention by sulfation with sulfuric acid, chlorosulfonic acid, sulfur trioxide. dioxanesulfur trioxide or other adducts of sulfur trioxide. The reaction mixture comprising the first derivative as the main component can be used for sulfation to produce an improved detergent, or the pure first derivative may be separated by distillation and then sulfated.

TABLE II LONG CHAIN ETHER ALCOHOLS FROM- PROPYLENE OXIDE AND 1,2BUTYLENE OXIDE ANALYSIS Freezing 60 Found Theory Point n,, %C C C C,,,l-I OCH,CHOHCH 73.59 13.13 73.71 13.20 25 1.4269 C,,H,,[OCH CH(CH,)] OH 71.56 12.57 71.47 12.66 15 1.4278 C H OCH CHOHCH 74.88 13.15 74.94 13.32 33 1.4387 C H, [OCH CH(CH )],OH 72.44 12.66 72.67 12.81 3 1.4307 C H OCH CHOHCH 76.25 13.56 75.93 13.42 39 1.4330 C H [OCH CH(CH )],0H 73.68 12.72 73.68 12.93 19 1.4330 C ,H -,-,OCH,CHOHCH;, 76.86 13.42 76.76 13.50 41 1.4352 C ,.H l0CH-,CH(CH )],OH 74.74 12.92 74.55 13.04 30 1.4348 C H OCH CHOHC H 74.15 13.11 74.36 13.26 1 1.4270 C H,,,IOCH CH(C,H,)],OH 72.76 12.81 72.67 12.81 28 1.4301 C H OCH CHOHQH 75.47 13.32 75.46 13.37 14 1.4311 C,,H ,,[OCH,CH(C H,,) OH 73.80 12.72 73.68 12.93 8 1.4325 c..,1-1 ocincuonc u 76.08 13.23 76.37 13.46 26 1.4337 C H [OCH,CH(C H.-,) Ig 74.37 12.91 74.55 13.04 .10 1.4344 C H OCH CHOHC H 77.12 13.49 77.12 13.53 36 1.4357 C ,.H ,[OCH CH(C H,) l OH 75.39 13.19 75.30 13.13 19 1.4363

The ether alcohols of the present invention can be converted to water soluble nonionic detergents by fur- TABLE TIL-FREEZING FOEINTS 0F .EIIIER ALCOHOLS I-Ioxadecanol Octudocunol First Second l lrsl. S0001 1(1 Alkylnne oxidev derivntlvu dorlvnlivv dorlvnlivv ill-rlvnllvn I2 0 TL 31) 1t) 41 30 C HaI-C H2 Alternatively the reaction mixture can be distilled to remove only the unreacted parent alcohol, prior to sulfation of the remaining reaction mixture. Analyses for sodium and sulfur on the pure ether alcohol sulfates of our invention are shown in Table IV. The ether alcohol 6 The ether alcohol sulfates also show good detergency when used in the form of built solutions in hard water (Table V, fourth column). The particular composition of the builder, described in a footnote to Table V, is not 5 intended to be a limiting factor. Other combinations sulfates have melting points or melting point ranges and ratios of the inorganic salts are. used in convenwhich may be observed under a hot stage microscope tional builders, often without the carboxymethyland these are also shown in Table IV. cellulose. Foam height is lowered by oxyalkylation,

Ether alcohol sulfates containing one oxyethyl group particularly for tallow alcohol derivatives, and this may [-OCH CH melt higher than corresponding ether al- 10 be a desirable feature to avoid excessive foaming durcohol sulfates having an oxypropyl group ing washing operations. The process to provide the OCH CH(CH which in turn melt higher than those products of the present invention, oxyalkylation with with one oxybutyl group, [-OCH CH(C H Ether propylene oxide or butylene oxide. followed by sulfaalcohol sulfates having two oxypropyl or oxybutyl tion, therefore results in improvements over the parent groups have still lower melting points as is evident in alcohol sulfate with increased general usefulness as a Table IV. In general ether alcohol sulfates of lower. result of greater solubility and the ability to disperse melting point are more soluble. soap in hard water.

The ether alcohol sulfates of our invention are very soluble in water, particularly those derived from The Crltlcal 66 6 C0nCentrati0n (time), the condodecanol and tetradecanol. For example the sulfated Fentratlon at Whlch "h begin to form hP monoxypropylated derivative from tetradecano] is so]- [Oils and molecules, 15 a fundamental CharaCterlStlC Of uble up to a concentration of percent at which con- Surface actlv agents, dependent P mhlechlaf h Centration i forms a clear l at room temperature ture. In Table V the cmc decreases with increasing size The surface active properties of the pure ether alco- 0f the y y g p and the degree of oxyalkylatlohhol sulfates of our invention are shown in Table V. The 5 increased solubility of the ether alcohol sulfates is evi- It 15 not necfissary t P the lhdhhdhal Ether d i h lower K fft point f h cxypropyl and cohol by fractional distillation or other devices in order butyl derivatives. The values for lime soap dispersing t0 Ph the Objects P our lhvehtloh- The ehth'e power are about 10 percent Thi i hi hl d i bl reaction mixture, which will conta n unreacted parent and means that only about 10 grams or less of the ether 30 alcohol, a major Portloh of the first denvathfi alcohol sulfate are required to disperse the calcium Smaller amounts of sffcondary and further f Y soap formed from 100 grams of sodium oleate. Thus y he t t0 gh/e a detergent p h Wlth h the compounds of our invention are useful with soap in Proved sohlhlhty and general hsefulhess- It also P hard water. ble to separate the parent TABLE IV ANALYSIS AND MELTING POINT OF ETHER ALCOHOL SULFATES Na S Melting" 0111! found theory found theory C,,H,,OCH,CH(CH;)OSO,N-a 6.68 6.64 9.29 9.26 l37-l42 C,,H, [0CH,CH(CH )},SO,Na 5.90 5.68 7.96 7.93 87-93 c ii pciixmcii osoma 6.05 6.14 8.28 8.56 139-140" C H IOCH,CH(CH3)l Oso Na 5.47 5.32 7.75 7.41 82-87 C, H OCH,CH(CH,)OSO Na 5.63 5.71 7.72 7.97 131 133 C, H ,]OCH,CH(CH;)]=0SO; Na 4.90 4.99 7.11 6.96 81-84" C,,,H,,0CH,CH(CH,)0S0,N6 5.34 5.34 7.37 7.45 134-137 C, H -1lOCH,CH(CH,)],OSO Na 4.71 4.71 6.44 6.56 s0-82 c ti ocmctiic i-mosoma 6.34 6.38 9.04 8.90 77412 C,,i-i,,,0cii,CH(C,ii,1oso,Na 5.86 5.92 8.19 8.25 74-76 C|4H2 lOCH:CH(CgH5)ljosoaNa 4.82 4.99 6.80 6.96 Liquid at room 0 temperature C, H 0CH,CH(C,H,)OSO Na 5.60 5.52 7.89 7.70 84-85 C,,H;,,[OCH,CH(C,H,)1,0SO,N:1 4.69 4.71 6.78 6.56 Liquid at room temperature Hot stage microscope. For comparison the melting point urc m ogmosomu is 189-187".

TABLE V SURFACE ACTIVE PROPERTIES OF PURE ETHER ALCOHOL SULFATES cinc, Krafft Lime Detergency Foam millipoint soap Alb, 05% height, 05% moles l% sol. disp. +.2% +.2% per liter C. power builder builder ppm. p.p.m., mm.

C,,H, OCH,CH(CH,)OSO Na 2.69 clear 14 22 210 TABLE V Continued SURFACE ACTIVE PROPERTIES OF PURE ETHER ALCOHOL SULFATES crnc. Krafft Lime Detergency Foam mil1ipoint soap Alb. 05% height. 05% moles 1% sol. disp. +.2% +.2% per liter C. power builder builder p.p.m. p.p.m.. mm.

C H [OCH,CH(CH,)]OSO Na 1.54 clear 6 21 205 at zero C H OCH,CH(CH )OSO Na 0.58 14 8 26 220 C H,,,[CH,CH(CH;)],OSO Na 0.36 clear 9 23 200 at zero C H OCH CH(CH (OSO=Na 0.16 27 8 27 185 C H IOCH CWCH )J OSO Na 0.076 19 7 26 175 C,,.H: OCH CH(CH;(OSO,Na c 43 8 28 100 C H lOCH CMCH OSO,Na 0.041 31 7 25 9O C, H ,OCH CH(C,H )OSO Na 1.8 clear 10 22 225 at zero C H lOCH-,CH(C H )],OSO Na 0.8 clear 10 21 210 at zero C H OCH,CH(C,H,)OSO Na 0.43 13 9 200 C H, lOCH,CH(C,H,)] OSO Na 0.20 clear 19 22 175 at zero C H OCH,CH(C H,)OSO Na 0.12 23 9 26 155 C,,,H, -,[OCH,CH(C,H,)],OSO Na 0.061 21 8 24 50 C,,.H OCH,CH(C H )OSO Na c 38 10 26 75 C,,,H; [OCH CH(C H )],OSO Na 0.051 24 11 26 35 C,,H,,OSO;,Na 6.8 16 18 185 C H OSO Na c 56 c 28 190 C H oCH CH Oso Na 0.11 46 9 29 100 Critical Micella Concentration Ar=incrcase in reflectance after washing standard soiled cotton in the Targo-O-Teretcr. Bui1dcF55'71 Nu,P

NaJf' 10% Na mctasilicate. 1'1 carboxymethylccllulose. Not soluble enough for the test conditions unreacted alcohol and return it to the oxyalkylation stefi andto sulfate the remaining o xyalkylated reaction product containing the first derivative as the major component. The surface active properties of the unseparated ether alcohol sulfates of our invention are shown in Table V1. The mixtures shown are direct sulfation products from the oxyalkylation reaction mixture, except for 4, which is the sulfation product after parent alcohol and the first derivative have been removed by distillation. As a result of the loss of the first derivative, detergency and foam height is decreased but the product has excellent lime soap dispersing properties. The properties of the direct sulfation mixtures compare well with those of the individual ether alcohol sulfates of Table V.

As shown in Table V], l and 7, mixtures containing mono-oxyalkylated parent alcohol can have an average J 24.4 Nu,s0., 10%

value of n which is less than 1. While the means of producing mixtures of ether alcohol sulfates with considerably higher or lower average values of n than those of Table V1 will be apparent from the foregoing discussion, the preferred values for n are in the range of about 0.9 to 2.5.

The ease of biodegradation of the ether alcohol sulfate detergents was measured in the river water test. Detergent solutions containing 5 ppm of detergent in Schuylkill River water were stored in the dark at 20 C and aliquots were analyzed regularly by the Methylene Blue method [J. K. Weil and A. J. Stirton, J. Am. Oil Chemists Soc. 41, 5,355358(1964)]. The time for 80 percent degradation, from 5 ppm to 1 ppm, was noted and is recorded in Table V11, compared to the TABLE VI SURFACE ACTIVE PROPERTIES OF ETHER ALCOHOL SULFATE MIXTURES Average Lime Detergency. Foam height. number soap 0.05% 0.2% 0.05% 0.2% of disp. builder, builder. 60 oxyalkyl power, 300 p.p.m. 300 p.p.m. groups, R mm. n

1. c H lOCl-hCHtCHal1,,OS(),Na 0.92 17 27 210 2. C H loCl hCHlCH )l,,OSO Nn 1.74 10 26 220 3. C.,,H,,,|OCH,CH(CH,)l OsO Nn 1.20 7 27 I 5. c m ocmcmgn lbosom 1.30 12 24 Parent alcohol and first derivative removed by distillation. prior to sulfation TABLE V11 BASE OF BIODEGRADATION Standard pure sodium dodecanesulfonatc Linear alkylhenzcnesulfonate Branded chain alkylbcnzenesulfonale standard sodium dodecanesulfonate, linear alkylbenzenesulfonate, and branched chain alkylbenzenesulfonate. It is evident the ether alcohol sulfates of our invention, from propylene oxide and 1.2-butylene oxide, are very soft detergents, 100 percent degraded in less than 3 days.

While the ether alcohol sulfates are typically prepared as the sodium derivatives, the sulfation mixture can be neutralized with other alkaline reagents than NaOH. Reagents such as KOH, LiOH, NH OH and NH(C H.,OH) OH can be used to obtain the K, Li, NH or NH(C H OH) derivative.

The nature of our invention can be further understood from the examples which follow which illustrate, but are not intended to limit, the scope of the present invention.

EXAMPLE 1 2-Octadecyloxy-l-methylethanol and Sodium 2- Octadecyloxy-l-methy1ethyl Sulfate Octadecanol, 128 grams (0.474 moles), and 0.6 g. of KOH were heated to 150C. Liquid propylene oxide, 31.8 g. (0.548 moles), was added dropwise with stirring under an efficient reflux system to retain unreacted propylene oxide. During the addition, which took 30 minutes, the temperature was maintained between 145-150C. The alkaline catalyst was neutralized with 1.0 ml. of concentrated hydrochloric acid and inorganic salt was washed from an ethereal solution of the product with water. The residue from the ethereal solution was fractionally distilled to give pure C H OCH CHOHCH (b.p. 154C at 0.2 mm g) (Table 11, item 7).

The pure ether alcohol, g. (0.061 moles) was dis solved in 100 ml. of CCl, and chilled to 0C. Chlorosulfonic acid was added dropwise with stirring and the temperature was allowed to rise to C. The sulfation mixture was rechilled to 0C., diluted with an equal volume of cold ethanol and neutralized with 18 N NaOH. The product, an ether alcohol sulfate, was crystallized from the neutralized reaction mixture at -20C. and recrystallized from absolute ethanol at 0C. to give an 87 percent yield of pure C H OCH CH(CH )OSO Na with the analysis shown in Table IV, item 7.

EXAMPLE 2 Sulfation of Oxypropylated Octadecanol Reaction Mixture Octadecanol, 228 g. (0.844 moles), and 1.2 g. of KOH were heated to 160C. and 66 g. 1.14 moles) of propylene oxide was added dropwise during 1.5 hours, keeping the mixture at 160175C. under efficient reflux to retain propylene oxide. The catalyst was neutralized with 1.75 ml. of concentrated HCl, 1, the product was dissolved in ethyl ether, washed free of inorganics, and ether was removed on the steam bath. Analysis of a sample of the reaction mixture by conversion to the acetate ester and gas-liquid chromatography on 20 percent silicone gum rubber column at 280C. gave the following composition in mole percent: unreacted CIBHMOH, CmHznOCHgCHOHCHg, C18H37[OCH2CH(CH3)]2OH, 2 l C H [OCH CH(CH OH, 6.3. The average number of oxypropyl groups added per mole of octadecanol was 1.12.

A 10 percent molar excess of chlorosulfonic acid was added dropwise to a stirred solution of the o xypropylation reaction product in cold CCl The reaction mixture was allowed to warm to room temperature, diluted with an equal volume of cold ethanol and neutralized with 18 N NaOH. Evaporation of solvents gave an amorphous solid C, H [OCH CH(*CH OSO Na, percent active ingredient, with the properties shown in Table V1 (6).

EXAMPLE 3 EXAMPLE 4 2-Octadecy1oxy-1-ethylethanol and Sodium 2- Octadecyloxy- 1 -ethyethyl Sulfate Fractional distillation of a portion of the reaction mixture of Example 3 separated the first derivative as C H OCH CHOHC H b.p. l74-l76C at 0.33 mm Hg. pressure, purity 97 percent by GLC, with the elemental analysis and physical constants shown in Table 11. The pure ether alcohol was sulfated as described in Example 1 to give C, 1-l OCH CH(C H )OSO Na with elemental analysis shown in Table IV and surface active properties shown in Table V EXAMPLE 5 l,4-Diethy1-3,6-Dioxatetracosanol and Sodium 1 ,4-Diethy1-3,6-Dioxatetracosanyl Sulfate Fractional distillation of a portion of the reaction mixture of Example 3 separated the second derivative as C H [OC1-l CH(C H OH, b.p. 197203C. at 0.35 mm Hg, purity 98 percent by CLC, with the elemental anaylsis and physical constants shown in Table 11. The pure ether alcohol was sulfated as described in Example 1 to give C, H [OCH CH(C H OSO Na with elemental analysis shown in Table IV (15).

EXAMPLE 6 EXAMPLE 7 i 2-Hexadecyloxy-1-ethy1ethanol and Sodium 2-Hexadecyloxy-l-ethylethyl Sulfate Fractional distillation of a reaction mixture similar to I that described in Example 6 separated the first derivative as C H OCH CHOHC H b.p. 141-142C. at 0.16 mm hg., purity 99 percent by CLC, with the elemental analysis and physical constants shown in Table .11. The pure ether alcohol was sulfated as described in Example 1 to give C H OCH CH(C H )OSO Na with elemental analysis shown in Table IV and surface active properties shown in Table V (13).

EXAMPLE 8 Sulfation of Oxypropylated Hexadecanol Reaction Mixture Propylene oxide was added to hexadecanol under alkaline catalysis as described in Example 2. Gas-liquid chromatographic analysis of the acetate ester gave the following composition in mole C, H OH 19.9; C, H OCH CHOHCH 49.5; C, H [OCH CH(CH l OH 22.5 C H [OCH CH(CH OH 6.5; C, H [OCH CH(CH OH 1.2.

The average number of oxypropyl groups was 1.20. The reaction mixture was sulfated as described in Example 2 and the properties of the sulfation product C, H [OCH CH(CH OSO Na are shown in Table V1 (3).

EXAMPLE 9 2-Hexadecy1oxy-l-methylethanol and Sodium 2-Hexadecyloxy- 1 -methy1ethyl Sulfate Fractional distillation of a portion of the reaction mixture of Example 8 separated the first derivative as C H OCH CHOHCH b.p. 123-124C. at 0.08 mm Hg, with the elemental analysis and physical constants shown in Table 11. The pure ether alcohol was sulfated as described in Example 1 to give C H OCH CmCH- )OSO Na with elemental analysis shown in Table IV and surface active properties shown in Table V (5).

EXAMPLE l0 Sulfation of Oxypropylated Tetradecanol Reaction Mixture Propylene oxide, 47 g. (0.81 moles), was added to g. (0.725 moles) of tetradecanol under alkaline catalysis as described in Example 2. Gas-liquid chromatographic analysis of the acetate ester showed the following composition in mole%: C H OH 5.5; C H OCH CHOHCH 39.7; C H [OCH CH(CH OH 34.7; C, H [OCH CH(CH 1 01-1 15.8; C, H [OCH CH(CH OH 4.4 The average number of oxypropyl groups was 1.74. The reaction product was sulfated as described in Example 2 to give C, H [OCH CH(CH .,OSO Na with the surface active properties shown in TableVl (2). The reaction product prior to sulfation may be fractionally distilled to separate the first and second derivatives (Table 11) which can be sulfated to give the ether alcohol sulfates of Table V (3, 4).

EXAMPLE 1 1 Sulfation of Oxypropylated Dodecanol Reaction Mixture Propylene oxide 47 g. (0.81 moles) was added to 153 g. (0.823 moles) of dodecanol under alkaline catalysis as described in Example 2. Gas-liquid chromatographic analysis of the acetate ester showed the following compOSitiOn in mole C12H25OH C12H25OCH2. CHOHCHg 54.4; C H [OCH CH(CH O1-1 14.4; C12H25[OCH2CH(CH3)]3OH C, H [OCl-l CH(CH )],OH 0.3 The average number of oxypropyl groups was 0.92. The reaction. product was sulfated as described in Example 2 to give C12H25[OCH2CH(CH3)10320SO3N3 thfi Surface aC- tive properties shown in Table V] (1). The reaction product prior to sulfation may be fractionally distilled to separate the first derivative (Table 11) which can be sulfated to give the ether alcohol sulfate of Tables 1V (1) and V (1).

We claim:

1. A compound of the formula 

1. A COMPOUND OF THE FORMULA 